Chemical solution, method for producing modified substrate, and method for producing laminate

Abstract

The present invention provides a chemical solution capable of forming a coating film capable of suppressing deposition of a material by ALD treatment. This chemical solution is used in the production of a semiconductor, and contains a silylating agent, an aprotic solvent, and an alcohol, the alcohol content being 5-200 ppm by mass relative to the total mass of the chemical solution.

Description

Technical Field

[0001] The present invention relates to a chemical solution, a method for producing a modified substrate, and a method for producing a laminate. Background Art

[0002] As semiconductor devices become increasingly miniaturized, it is required to form even finer and more precise semiconductor elements. Conventionally, photolithography has been used to form semiconductor elements, but it is unable to meet the accuracy required recently due to pattern alignment errors and the like.

[0003] Therefore, as a method for forming a semiconductor element, a method has been studied in which a film composed of a compound is selectively formed by adsorbing the compound selectively on a region composed of a specific material, and the film is used to process a region other than the specific material.

[0004] Specifically, for example, a method has been devised in which a film that inhibits deposition of a material is selectively formed on a specific region and then an atomic layer deposition (ALD) process is performed to selectively deposit a material in a region where the film does not exist.

[0005] As a chemical solution capable of forming a film as described above, Patent Document 1 discloses a water-repellent protective film-forming chemical solution containing a specific silicon compound as a water-repellent protective film-forming agent.

[0006] Previous technical literature

[0007] Patent Literature

[0008] Patent Document 1: Japanese Patent Application Publication No. 2012-178431 Summary of the invention

[0009] Technical issues to be solved by the invention

[0010] The inventors have found that when a film is formed using the chemical solution described in the above document and a material is deposited on the film by an ALD process, the amount of material deposited on the film is large and this needs to be improved.

[0011] Therefore, an object of the present invention is to provide a chemical solution capable of forming a film that can suppress the deposition of materials by ALD processing, and also to provide a method for producing a modified substrate and a method for producing a laminate using the chemical solution.

[0012] Means for solving technical problems

[0013] The present inventors have conducted intensive studies to solve the above-mentioned problems, and have found that the problems can be solved by the following configuration.

[0014] [1] A chemical solution used in semiconductor production, comprising a silylation agent, an aprotic solvent, and an alcohol, wherein the content of the alcohol is 5 to 200 ppm by mass based on the total mass of the chemical solution.

[0015] [2] The drug solution according to [1], wherein:

[0016] The silylating agent includes a compound having a Si—N bond.

[0017] [3] The drug solution according to [1] or [2], wherein:

[0018] The silylating agent contains a silazane compound or a compound represented by the formula (1) described later.

[0019] [4] The drug solution according to any one of [1] to [3], wherein

[0020] The silylating agent contains a silazane compound.

[0021] [5] The drug solution according to any one of [1] to [4], wherein

[0022] The chemical solution further contains water, and the content of the water is 100 ppm by mass or less relative to the total mass of the chemical solution.

[0023] [6] The drug solution according to any one of [1] to [5], wherein

[0024] The alcohol has 10 or less carbon atoms.

[0025] [7] The drug solution according to any one of [1] to [6], wherein

[0026] The above alcohol has two or more hydroxyl groups.

[0027] [8] The drug solution according to any one of [1] to [7], wherein

[0028] The content of the alcohol is 5 to 150 ppm by mass based on the total mass of the chemical solution.

[0029] [9] A chemical solution used in the manufacture of a semiconductor, comprising:

[0030] a compound selected from the group consisting of a silazane compound, a compound represented by the formula (1) described below, and an alkoxysilane compound, an aprotic solvent, and an alcohol,

[0031] The content of the alcohol is 5 to 200 ppm by mass based on the total mass of the chemical solution.

[0032]

[10] The chemical solution according to any one of [1] to [9], which is used for treating a substrate having at least two regions on its surface made of different materials.

[0033]

[11] A method for manufacturing a modified substrate, comprising step 1, in which a substrate having a region formed of an insulator is brought into contact with a chemical solution described in any one of [1] to

[10] to form a film containing silicon atoms on the region formed of the insulator.

[0034]

[12] The method for producing a modified substrate according to

[11] , wherein:

[0035] The above-mentioned insulator is a metal oxide.

[0036]

[13] The method for producing a modified substrate according to

[11] or

[12] , further comprising, after the step 1, a step 2, in which the substrate having the film containing the silicon atoms is subjected to a rinsing treatment.

[0037]

[14] A method for manufacturing a stacked body, comprising step 3, in which an atomic layer deposition process is performed on a modified substrate manufactured using any one of the manufacturing methods described in

[11] to

[13] to form a metal film, a metal oxide film or a metal nitride film on an area other than an area where a film containing the above-mentioned silicon atoms is formed.

[0038]

[15] The method for producing a laminate according to

[14] , further comprising, after the step 3, a step 4 in which the film containing the silicon atoms is removed.

[0039] Effects of the Invention

[0040] According to the present invention, a chemical solution capable of forming a film capable of suppressing deposition of a material by an ALD process can be provided. In addition, according to the present invention, a method for producing a modified substrate and a method for producing a laminated body using the chemical solution can be provided. DETAILED DESCRIPTION

[0041] Hereinafter, the present invention will be described in detail.

[0042] Although the description of the constituent elements described below may be made based on representative embodiments of the present invention, the present invention is not limited to these embodiments.

[0043] In the present specification, a numerical range expressed using "to" means a range including the numerical values ​​described before and after "to" as the lower limit and the upper limit.

[0044] In this specification, "ppm" means "parts-per-million (10-6 ): parts per million, "ppb" means "parts-per-billion (10 -9 ): parts per billion, "ppt" means "parts-per-trillion (10 -12 ): parts per trillion.

[0045] In the present specification, when two or more kinds of a certain component are present, the "content" of the component means the total content of these two or more kinds of components.

[0046] In this specification, when there are multiple substituents and linking groups represented by specific symbols (hereinafter referred to as substituents, etc.) or when multiple substituents, etc. are specified at the same time, the respective substituents, etc. may be the same or different from each other. The same applies to the number of substituents, etc.

[0047] [Medicine]

[0048] Hereinafter, the medicinal solution of the present invention will be described in detail.

[0049] A chemical solution according to a first aspect of the present invention is a chemical solution used in semiconductor production, and contains a silylation agent, an aprotic solvent, and an alcohol, wherein the content of the alcohol is 5 to 200 ppm by mass based on the total mass of the chemical solution.

[0050] The second embodiment of the chemical solution of the present invention is a chemical solution used in the manufacture of semiconductors, which contains a compound selected from silazane compounds, compounds represented by formula (1) described later, and alkoxysilane compounds (hereinafter also referred to as "specific silicon compounds"), an aprotic solvent and an alcohol, wherein the content of the alcohol is 5 to 200 ppm by mass relative to the total mass of the chemical solution.

[0051] In the present specification, when simply referred to as "the drug solution of the present invention", unless otherwise specified, it is a concept that includes both the first embodiment and the second embodiment of the drug solution.

[0052] The reason why the drug solution having the above-mentioned structure can solve the problems of the present invention is not clear, but the present inventors speculate as follows.

[0053] In addition, the mechanism by which the effect can be obtained by the following speculation is not limited. In other words, even if the effect is obtained by a mechanism other than the following, it is also included in the scope of the present invention.

[0054] The higher the hydrophobicity of the material surface, the more the deposition of the material based on the ALD treatment can be suppressed. The silylating agent or specific silicon compound contained in the chemical solution reacts with the functional groups existing on the surface of the object to be formed (hereinafter also referred to as the "modified substrate") to form a film containing highly hydrophobic silicon atoms. At this time, the content of alcohol in the chemical solution is below a specific amount, so that the silylating agent or specific silicon compound will not be deactivated by the reaction with the alcohol, and a film can be formed, so a hydrophobic film can be formed with a high coverage rate.

[0055] Furthermore, by containing a specific amount or more of alcohol, a film formed by the interaction between the alcohol and the modified substrate can be formed in the region where the film based on the silylating agent or the specific silicon compound is not formed. Thus, the deposition of the material with the region where the film based on the silylating agent or the specific silicon compound is not formed as the core can be suppressed.

[0056] As a result, it is thought that the chemical solution of the present invention can form a film that can suppress the deposition of materials by the ALD process.

[0057] Hereinafter, the chemical solution of the present invention will be simply referred to as “chemical solution.” Furthermore, the fact that the deposition of the material by the ALD process can be further suppressed will also be referred to as “the effect of the present invention is more excellent.”

[0058] 〔Silylating agent〕

[0059] The chemical solution according to the first aspect of the present invention contains a silylation agent.

[0060] The silylating agent is a compound that can react with a functional group present on the surface of the modified substrate to introduce a silyl group. Examples of the functional group include a hydroxyl group, an amino group, a carboxyl group, and an amide group.

[0061] Examples of the silylating agent include compounds having a Si—N bond and silylating agents represented by the formula (3) described below.

[0062] <Compounds having Si-N bonds>

[0063] The silylating agent preferably has a Si—N bond. That is, the silylating agent is preferably a compound having a Si—N bond.

[0064] The number of Si—N bonds in the compound having Si—N bonds is preferably 1 to 4, more preferably 2 to 3, and even more preferably 2.

[0065] The number of carbon atoms in the compound having a Si—N bond is not particularly limited, but is preferably 1 to 25, more preferably 2 to 15, and even more preferably 3 to 12.

[0066] Examples of the compound having a Si—N bond include a compound represented by formula (1) and a silazane compound.

[0067] [Chemical formula 1]

[0068]

[0069] In formula (1), R 1 Each independently represents a hydrocarbon group (monovalent hydrocarbon group) which may have a halogen atom.

[0070] The hydrocarbon group preferably has 1 to 25 carbon atoms.

[0071] Examples of the hydrocarbon group include an alkyl group, an alkenyl group, and an aryl group.

[0072] The alkyl group may be any of a linear, branched, and cyclic group, and is preferably a linear group. The number of carbon atoms in the linear or branched alkyl group is preferably 1 to 18, more preferably 1 to 6, further preferably 1 to 4, and particularly preferably 1 or 2. Examples of the linear or branched alkyl group include methyl, ethyl, n-propyl, isopropyl, butyl, sec-butyl, tert-butyl, n-hexyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl groups, and are preferably methyl, ethyl, n-propyl, n-butyl, or tert-butyl groups, and more preferably methyl or ethyl groups.

[0073] The number of carbon atoms in the cyclic alkyl group (cycloalkyl group) is preferably 3 to 18, more preferably 3 to 12, and still more preferably 3 to 6. Examples of the cycloalkyl group include a cyclopropyl group and a cyclohexyl group.

[0074] The number of carbon atoms in the alkenyl group is preferably 2 to 12, more preferably 2 to 6, and even more preferably 2 to 4. Examples of the alkenyl group include vinyl and allyl groups.

[0075] The number of carbon atoms in the aryl group is preferably 5 to 8, more preferably 5 to 6. Examples of the aryl group include a phenyl group.

[0076] Examples of the halogen atom which the monovalent hydrocarbon group may have include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferred. When the monovalent hydrocarbon group has a halogen atom, for example, the alkyl group may be a perfluoroalkyl group.

[0077] As R 1 The group represented is preferably an alkyl group having 1 to 25 carbon atoms which may have a halogen atom, more preferably a linear alkyl group having 1 to 18 carbon atoms which may have a halogen atom, and still more preferably a linear alkyl group having 1 to 6 carbon atoms which may have a halogen atom.

[0078] In R 1 When there are multiple R 1 The groups represented may be the same or different.

[0079] R 2 Each independently represents a hydrogen atom, a hydrocarbon group which may have a halogen atom, or an acyl group which may have a halogen atom (R—CO—; R represents a hydrocarbon group which may have a halogen atom).

[0080] The hydrocarbon group preferably has 1 to 18 carbon atoms.

[0081] Examples of the hydrocarbon group include an alkyl group and an aryl group.

[0082] The alkyl group may be any of a linear, branched, and cyclic group. The number of carbon atoms of the linear or branched alkyl group is preferably 1 to 6, more preferably 1 to 4, and further preferably 1 or 2. Examples of the linear or branched alkyl group include methyl, ethyl, n-propyl, isopropyl, butyl, sec-butyl, tert-butyl, n-hexyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl, preferably methyl, ethyl, n-propyl, or n-butyl, and more preferably methyl or ethyl.

[0083] The number of carbon atoms in the cyclic alkyl group (cycloalkyl group) is preferably 3 to 12, more preferably 3 to 6. Examples of the cycloalkyl group include a cyclopropyl group and a cyclohexyl group.

[0084] The number of carbon atoms in the aryl group is preferably 5 to 8, more preferably 5 to 6. Examples of the aryl group include a phenyl group.

[0085] Furthermore, examples of the halogen atom which the hydrocarbon group may have include fluorine atom, chlorine atom, bromine atom, iodine atom, etc., and fluorine atom is preferred. When the monovalent hydrocarbon group has a halogen atom, for example, the alkyl group may be a perfluoroalkyl group.

[0086] The definition and preferred embodiment of the hydrocarbon group which may have a halogen atom contained in the above acyl group are similar to those which may have the above R 2 The hydrocarbon groups of the halogen atoms represented are the same.

[0087] As R 2 The group represented is preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms which may have a halogen atom, or an acyl group having 2 to 4 carbon atoms which may have a halogen atom, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, further preferably a hydrogen atom or a methyl group.

[0088] There are multiple R 2 The groups represented may be the same or different.

[0089] a represents an integer of 1 to 3, preferably 2 or 3, more preferably 3.

[0090] Examples of the compound represented by formula (1) include C4H9(CH3)2SiN(CH3)2, C5H 11(CH3)2SiN(CH3)2, C6H 13 (CH3)2SiN(CH3)2, C7H 15 (CH3)2SiN(CH3)2, C8H 17 (CH3)2SiN(CH3)2, C9H 19 (CH3)2SiN(CH3)2, C 10 H 21 (CH3)2SiN(CH3)2, C 11 H 23 (CH3)2SiN(CH3)2, C 12 H 25 (CH3)2SiN(CH3)2, C 13 H 27 (CH3)2SiN(CH3)2, C 14 H 29 (CH3)2SiN(CH3)2, C 15 H 31 (CH3)2SiN(CH3)2, C 16 H 33 (CH3)2SiN(CH3)2, C 17 H 35 (CH3)2SiN(CH3)2, C 18 H 37 (CH3)2SiN(CH3)2, and C 30 H 61 (CH3)2SiN(CH3)2 and other alkyldimethyl(dimethylamino)silanes; C5H 11 (CH3)HSiN(CH3)2, C6H 13 (CH3)HSiN(CH3)2, C7H 15 (CH3)HSiN(CH3)2, C8H 17 (CH3)HSiN(CH3)2, C9H 19 (CH3)HSiN(CH3)2, C 10 H 21 (CH3)HSiN(CH3)2, C 11 H 23 (CH3)HSiN(CH3)2, C 12 H 25 (CH3)HSiN(CH3)2, C 13 H 27 (CH3)HSiN(CH3)2, C 14 H 29 (CH3)HSiN(CH3)2, C 15 H31 (CH3)HSiN(CH3)2、C 16 H 33 (CH3)HSiN(CH3)2、C 17 H 35 (CH3)HSiN(CH3)2、C 18 H 37 (CH3)HSiN(CH3)2, and C 30 H 61 (CH3)HSiN(CH3)2 and other alkylmethyl(dimethylamino)silanes; C2F5C2H4(CH3)2SiN(CH3)2, C3F7C2H4(CH3)2SiN(CH3)2, C4F9C2H4(CH3)2SiN(CH3)2, C5F 11 C2H4(CH3)2SiN(CH3)2、C6F 13 C2H4(CH3)2SiN(CH3)2、C7F 15 C2H4(CH3)2SiN(CH3)2, and C8F 17 Fluoroalkylmethyl(dimethylamino)silanes such as C2H4(CH3)2SiN(CH3)2; N-(alkyldimethylsilyl)-N-methylacetamides such as (CH3)3SiN(CH3)COCH3 and C4H9(CH3)2SiN(CH3)COCH3; (CH3)3SiN(CH3)COCF3 (N-methyl-N-trimethylsilyltrifluoroacetamide: MSTFA) and C4H9(CH3)2SiN(CH3)COCF3 (N-methyl Compounds in which the methyl groups in alkyldimethyl(dimethylamino)silane, alkylmethyl(dimethylamino)silane, fluoroalkylmethyl(dimethylamino)silane, N-(alkyldimethylsilyl)-N-methylfluoroacetamide and N-(alkyldimethylsilyl)-N-methylfluoroacetamide are replaced by alkyl groups having 1 to 18 carbon atoms, such as ethyl, propyl and butyl.

[0091] Among them, the compound represented by formula (1) is preferably C3H7(CH3)2SiN(CH3)2, C4H9(CH3)2SiN(CH3)2, C5H 11 (CH3)2SiN(CH3)2, C6H 13 (CH3)2SiN(CH3)2、C7H 15 (CH3)2SiN(CH3)2, C8H 17(CH3)2SiN(CH3)2, MSTFA or MTBSTFA, more preferably C4H9(CH3)2SiN(CH3)2.

[0092] The silazane compound is a compound having Si-N-Si bonds. The number of Si-N-Si bonds is not particularly limited, but is preferably 1 to 3, and more preferably 1.

[0093] The silazane compound is preferably a disilazane compound, and more preferably a compound represented by formula (2).

[0094] [Chemical formula 2]

[0095]

[0096] R 3 and R 4 Each independently represents a hydrocarbon group which may have a halogen atom.

[0097] R 3 and R 4 The definition and preferred embodiment of the hydrocarbon group represented by are the same as those of R in formula (1). 1 The hydrocarbon groups represented are the same.

[0098] In R 3 When there are multiple R 3 The groups represented by may be the same or different. 4 When there are multiple R 4 The groups represented may be the same or different.

[0099] R 5 represents a hydrogen atom or a hydrocarbon group which may have a halogen atom.

[0100] R 5 The definition and preferred embodiment of the hydrocarbon group represented by are the same as those of R in formula (1). 2 The hydrocarbon groups represented are the same.

[0101] As R 5 , preferably a hydrogen atom.

[0102] b and c each independently represent an integer of 1 to 3, preferably 2 or 3, and more preferably 2.

[0103] Examples of the silazane compound include tetramethyldisilazane (TMDS), hexamethyldisilazane (HMDS), tetraethyldisilazane, hexaethyldisilazane, tetrapropyldisilazane, hexapropyldisilazane, tetrabutyldisilazane and hexabutyldisilazane, preferably TMDS or HMDS, more preferably TMDS.

[0104] Examples of silazane compounds other than the above include [C4H9(CH3)2Si]2NH, [C5H 11 (CH3)2Si]2NH, [C6H 13 (CH3)2Si]2NH, [C7H 15 (CH3)2Si]2NH, [C8H 17 (CH3)2Si]2NH, [C9H 19 (CH3)2Si]2NH, [C 10 H 21 (CH3)2Si]2NH, [C 11 H 23 (CH3)2Si]2NH, [C 12 H 25 (CH3)2Si]2NH, [C 13 H 27 (CH3)2Si]2NH, [C 14 H 29 (CH3)2Si]2NH, [C 15 H 31 (CH3)2Si]2NH, [C 16 H 33 (CH3)2Si]2NH, [C 17 H 35 (CH3)2Si]2NH, [C 18 H 37 (CH3)2Si]2NH, [C2F5C2H4(CH3)2Si]2NH, [C3F7C2H4(CH3)2Si]2NH, [C4F9C2H4(CH3)2Si]2NH, [C5F 11 C2H4(CH3)2Si]2NH, [C6F 13 C2H4(CH3)2Si]2NH, [C7F 15 C2H4(CH3)2Si]2NH, [C8F 17 C2H4(CH3)2Si]2NH, [(C2H5)3Si]2NH, [C3H7(C2H5)2Si]2NH, [C4H9(C2H5)2Si]2NH, [C5H 11 (C2H5)2Si]2NH, [C6H 13 (C2H5)2Si]2NH, [C7H 15 (C2H5)2Si]2NH, [C8H 17 (C2H5)2Si]2NH, [C9H 19 (C2H5)2Si]2NH, [C 10 H21 (C2H5)2Si]2NH, [C 11 H 23 (C2H5)2Si]2NH, [C 12 H 25 (C2H5)2Si]2NH, [C 13 H 27 (C2H5)2Si]2NH, [C 14 H 29 (C2H5)2Si]2NH, [C 15 H 31 (C2H5)2Si]2NH, [C 16 H 33 (C2H5)2Si]2NH, [C 17 H 35 (C2H5)2Si]2NH and [C 18 H 37 (C2H5)2Si]2NH, etc.

[0105] Examples of the compound having a Si-N bond other than the above compounds include N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA) and N-trimethylsilylimidazole (TMSI).

[0106] <Compound represented by formula (3)>

[0107] As the silylating agent, a compound represented by the formula (3) is also preferred.

[0108] (R 6 ) d Si(H) e (X 1 ) 4-d-e (3)

[0109] In formula (3), R 6 Each independently represents a hydrocarbon group which may have a halogen atom.

[0110] R 6 The definition and preferred embodiment of the hydrocarbon group represented by are the same as those of R in formula (1). 1 The hydrocarbon groups represented are the same.

[0111] As R 6 The group represented is preferably an alkyl group which may have a halogen atom having 1 to 25 carbon atoms, and more preferably a linear alkyl group having 1 to 20 carbon atoms.

[0112] In R 6 When there are multiple R 6 The groups represented may be the same or different.

[0113] In R 6 If there are multiple R 6 The total number of carbon atoms of the groups represented is preferably 3-35, more preferably 3-25.

[0114] X 1 represents a hydrolyzable group. Examples of the hydrolyzable group include -OR 7 R 7 It represents a hydrocarbon group which may have a halogen atom.

[0115] R 7 The definition and preferred embodiment of the hydrocarbon group represented by are the same as those of R in formula (1). 2 The hydrocarbon groups represented are the same.

[0116] Examples of the halogen atom include a chlorine atom, a bromine atom and an iodine atom, and a chlorine atom is preferred.

[0117] As X 1 , preferably -OR 7 The alkoxy group is more preferred, and the alkoxy group having 1 to 3 carbon atoms is further preferred.

[0118] In X 1 If there are multiple X 1 The groups represented may be the same or different, but are preferably the same.

[0119] d represents an integer of 1 to 3, preferably 1 or 2, and more preferably 1.

[0120] e represents an integer of 0 to 2, and 0 is preferred.

[0121] d+e represents an integer of 1 to 3, preferably 1 or 2, and more preferably 1.

[0122] Examples of the silylating agent represented by the formula (3) include alkoxysilane compounds (X 1 A compound represented by the formula (3) in which the alkoxy group is present) and a chlorosilane compound (X 1 is a chlorine atom).

[0123] Examples of the alkoxysilane compound include CH3Si(OCH3)3, C2H5Si(OCH3)3, C3H7Si(OCH3)3, C4H9Si(OCH3)3, C5H 11 Si(OCH3)3、C6H 13 Si(OCH3)3、C7H 15 Si(OCH3)3、C8H 17 Si(OCH3)3、C9H 19Si(OCH3)3、C 10 H 21 Si(OCH3)3、C 11 H 23 Si(OCH3)3、C 12 H 25 Si(OCH3)3、C 13 H 27 Si(OCH3)3、C 14 H 29 Si(OCH3)3、C 15 H 31 Si(OCH3)3、C 16 H 33 Si(OCH3)3、C 17 H 35 Si(OCH3)3、C 18 H 37 Si(OCH3)3、C 20 H 41 Si(OCH3)3、C 24 H 49 Si(OCH3)3、(CH3)2Si(OCH3)2、C2H5Si(CH3)(OCH3)2、(C2H5)2Si(OCH3)2、C3H7Si (CH3)(OCH3)2、(C3H7)2Si(OCH3)2、C4H9Si(CH3)(OCH3)2、(C4H9)2Si(OCH3)2、C5H 11 Si(CH3)(OCH3)2、C6H 13 Si(CH3)(OCH3)2、C7H 15 Si(CH3)(OCH3)2、C8H 17 Si(CH3)(OCH3)2、C9H 19 Si(CH3)(OCH3)2、C 10 H 21 Si(CH3)(OCH3)2、C 11 H 23 Si(CH3)(OCH3)2、C 12 H 25 Si(CH3)(OCH3)2、C 13 H 27 Si(CH3)(OCH3)2、C 14 H 29 Si(CH3)(OCH3)2、C 15 H 31 Si(CH3)(OCH3)2、C 16 H 33Si(CH3)(OCH3)2, C 17 H 35 Si(CH3)(OCH3)2, C 18 H 37 Si(CH3)(OCH3)2, (CH3)3SiOCH3, C2H5Si(CH3)2OCH3, (C2H5)2Si(CH3)OCH3, (C2H5)3SiOCH3, C3H7Si(CH3)2OCH3, (C3H7)2Si(CH3)OCH3, (C3H7)3SiOCH3, C4H9Si(CH3)2OCH3, (C4H9)3SiOCH3, C5H 11 Si(CH3)2OCH3, C6H 13 Si(CH3)2OCH3, C7H 15 Si(CH3)2OCH3, C8H 17 Si(CH3)2OCH3, C9H 19 Si(CH3)2OCH3, C 10 H 21 Si(CH3)2OCH3, C 11 H 23 Si(CH3)2OCH3, C 12 H 25 Si(CH3)2OCH3, C 13 H 27 Si(CH3)2OCH3, C 14 H 29 Si(CH3)2OCH3, C 15 H 31 Si(CH3)2OCH3, C 16 H 33 Si(CH3)2OCH3, C 17 H 35 Si(CH3)2OCH3, C 18 H 37 Si(CH3)2OCH3, (CH3)2Si(H)OCH3, CH3Si(H)2OCH3, (C2H5)2Si(H)OCH3, C2H5Si(H)2OCH3, C2H5Si(CH3)(H)OCH3, and (C3H7)2Si(H)OCH3 and other alkylmethoxysilanes; CF3CH2CH2Si(OCH3)3, C2F5CH2CH2Si(OCH3)3, C3F7CH2CH2Si(OCH3)3, C4F9CH2CH2Si(OCH3)3, C5F 11 CH2CH2Si(OCH3)3, C6F 13CH2CH2Si(OCH3)3、C7F 15 CH2CH2Si(OCH3)3、C8F 17 CH2CH2Si(OCH3)3, CF3CH2CH2Si(CH3)(OCH3)2, C2F5CH2CH2Si(CH3)(OCH3)2, C3F7CH2CH2Si(CH3)(OCH3)2, C4F9CH2CH2Si(CH3)(OCH3)2, C5F 11 CH2CH2Si(CH3)(OCH3)2、C6F 13 CH2CH2Si(CH3)(OCH3)2、C7F 15 CH2CH2Si(CH3)(OCH3)2、C8F 17 CH2CH2Si(CH3)(OCH3)2, CF3CH2CH2Si(CH3)2OCH3, C2F5CH2CH2Si(CH3)2OCH3, C3F7CH2CH2Si(CH3)2OCH3, C4F9CH2CH2Si(CH3)2OCH3, C5F 11 CH2CH2Si(CH3)2OCH3、C6F 13 CH2CH2Si(CH3)2OCH3、C7F 15 CH2CH2Si(CH3)2OCH3、C8F 17 Fluoromethoxysilanes such as CH2CH2Si(CH3)2OCH3, and CF3CH2CH2Si(CH3)(H)OCH3; alkoxysilane compounds in which the methoxy groups in alkylmethoxysilane and fluoromethoxysilane are replaced by alkoxy groups having 2 to 10 carbon atoms.

[0124] Examples of the chlorosilane compound include trimethylchlorosilane (TMCS), triethylchlorosilane, tributylchlorosilane, triphenylchlorosilane, dimethyldichlorosilane (DMCS), tert-butyldimethylchlorosilane, dimethylphenylchlorosilane, and di-tert-butyldichlorosilane.

[0125] The silane compound represented by the formula (3) is preferably an alkoxysilane compound, more preferably an alkylmethoxysilane, and still more preferably an alkyltrimethoxysilane.

[0126] The silylating agent is preferably a compound having a Si—N bond or an alkoxysilane compound, more preferably a compound having a Si—N bond, further preferably a compound represented by formula (1) or a silazane compound, and particularly preferably a silazane compound.

[0127] The silylation agent may be used alone or in combination of two or more.

[0128] The content of the silylation agent is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and even more preferably 0.3 to 3% by mass, based on the total mass of the chemical solution.

[0129] (Specific silicon compounds)

[0130] The chemical solution of the second aspect of the present invention contains a specific silicon compound which is a compound selected from the group consisting of silazane compounds, compounds represented by formula (1), and alkoxysilane compounds.

[0131] The details and preferred embodiments of the silazane compound, the compound represented by the formula (1), and the alkoxysilane compound as the specific silicon compound are the same as those of the silazane compound, the compound represented by the formula (1), and the alkoxysilane compound described above.

[0132] The specific silicon compound may be used alone or in combination of two or more.

[0133] The content of the specific silicon compound is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and even more preferably 0.3 to 3% by mass, based on the total mass of the chemical solution.

[0134] 〔Aprotic solvent〕

[0135] The chemical solution of the first aspect and the second aspect of the present invention contains an aprotic solvent. An aprotic solvent is a solvent that does not have a proton-donating property.

[0136] Examples of the aprotic solvent include carbonate solvents, ester solvents, ether solvents, ketone solvents, hydrocarbon solvents, halogen-containing solvents, sulfoxide solvents, and nitrogen-containing solvents having no NH bond.

[0137] Examples of the carbonate solvent include propylene carbonate, dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate.

[0138] Examples of the ester solvent include ethyl acetate, propyl acetate, butyl acetate, methoxybutyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol diacetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol diacetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, triethylene glycol monobutyl ether acetate, triethylene glycol diacetate, tetraethylene glycol monomethyl ether acetate, tetraethylene glycol monoethyl ether acetate, tetraethylene glycol monobutyl ether acetate, tetraethylene glycol diacetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol diacetate, Chain ester solvents such as acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, dipropylene glycol diacetate, tripropylene glycol monomethyl ether acetate, tripropylene glycol monoethyl ether acetate, tripropylene glycol monobutyl ether acetate, tripropylene glycol diacetate, tetrapropylene glycol monomethyl ether acetate, tetrapropylene glycol diacetate and butanediol monomethyl ether acetate, and lactone solvents such as γ-butyrolactone, γ-valerolactone, γ-caprolactone, γ-heptanolactone, γ-octanolactone, γ-nonalactone, γ-decalactone, γ-undecalactone, γ-dodecalactone, δ-valerolactone, δ-caprolactone, δ-octanolactone, δ-nonalactone, δ-decalactone, δ-undecalactone, δ-dodecalactone and ε-caprolactone.

[0139] Examples of the ether solvent include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol dibutyl ether, triethylene glycol butyl methyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetraethylene glycol dibutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, and propylene glycol dibutyl ether. , dipropylene glycol dimethyl ether, dipropylene glycol methyl propyl ether, dipropylene glycol diethyl ether, dipropylene glycol dibutyl ether, tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether, tripropylene glycol dibutyl ether, tetrapropylene glycol dimethyl ether and butanediol dimethyl ether and other ethylene glycol dialkyl ether solvents, diethyl ether, dipropyl ether, ethyl butyl ether, dibutyl ether, ethyl amyl ether, diamyl ether, methyl cyclopentyl ether, ethylhexyl ether, dihexyl ether and dioctyl ether and other dialkyl ether solvents, and tetrahydrofuran and dibutylene glycol and other cyclic ether solvents.

[0140] Examples of the ketone solvent include acetone, acetylacetone, methyl ethyl ketone, methyl propyl ether ketone, methyl butyl ketone, cyclohexanone, and isophorone.

[0141] Examples of the hydrocarbon solvent include aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and tetralin; and aliphatic hydrocarbon solvents such as hexane, heptane, octane, and cyclohexane.

[0142] Examples of the halogen-containing solvent include perfluorooctane, perfluorononane, perfluorocyclopentane, perfluorocyclohexane, and hexafluorobenzene, perfluorocarbons such as 1,1,1,3,3-pentafluorobutane, octafluorocyclopentane, 2,3-dihydrodecafluoropentane, and ZEORORA H (manufactured by Zeon Corporation), methyl perfluoroisobutyl ether, methyl perfluorobutyl ether, ethyl perfluorobutyl ether, ethyl perfluoroisobutyl ether, AsahiKlin AE-3000 (manufactured by AGC Inc.), Novec 7100, Novec 7200, Novec 7300, and Novec 7600 (all manufactured by 3M Japan Limited), hydrofluoroethers such as tetrachloromethane, hydrochlorocarbons such as chloroform, chlorofluorocarbons such as dichlorodifluoromethane, 1,1-dichloro-2,2,3,3,3-pentafluoropropane, 1,3-dichloro-1,1,2,2,3-pentafluoropropane, 1-chloro-3,3,3-trifluoropropene and 1,2-dichloro-3,3,3-trifluoropropene, hydrochlorofluorocarbons such as perfluoroethers, and perfluoropolyethers.

[0143] Examples of the sulfoxide solvent include dimethyl sulfoxide.

[0144] Examples of the nitrogen-containing solvent having no NH bond include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, triethylamine, and pyridine.

[0145] The aprotic solvent is preferably a carbonate solvent, an ester solvent or an ether solvent, more preferably a carbonate solvent, a cyclic ester solvent or a glycol ether solvent, and still more preferably a carbonate solvent.

[0146] Among them, preferred are propylene carbonate, γ-butyrolactone, γ-valerolactone, PGMEA, ethylene glycol dibutyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol dimethyl ether or propylene glycol dibutyl ether, more preferred are propylene carbonate, γ-butyrolactone, γ-valerolactone, propylene glycol dimethyl ether or diethylene glycol dibutyl ether, and further preferred is propylene carbonate.

[0147] The aprotic solvent may be used alone or in combination of two or more. When two or more aprotic solvents are used in combination, it is preferred that the aprotic solvents are mixed.

[0148] The content of the aprotic solvent is preferably 90% by mass or more, more preferably 95% by mass or more, and further preferably 97% by mass or more relative to the total mass of the drug solution. The upper limit is less than 100% by mass, preferably 99.9% by mass or less, and more preferably 99.7% by mass or less.

[0149] 〔alcohol〕

[0150] The chemical solution in the first aspect and the second aspect contains alcohol.

[0151] The alcohol mentioned above is an organic compound having at least one alcoholic hydroxyl group.

[0152] The number of hydroxyl groups possessed by the alcohol may be 1 or more, preferably 2 or more. The upper limit is not particularly limited, but is preferably 6 or less, more preferably 4 or less.

[0153] The alcohol may be straight-chain or branched, and is preferably straight-chain. In addition, the alcohol may have a ring structure in the molecule.

[0154] The number of carbon atoms contained in the alcohol is not particularly limited, but is preferably 1 to 25, more preferably 1 to 15, further preferably 2 to 10, and particularly preferably 2 to 6 from the viewpoint of achieving more excellent effects of the present invention.

[0155] The molecular weight of the alcohol is not particularly limited, but from the viewpoint of more excellent effects of the present invention, it is preferably 300 or less, more preferably 200 or less, and further preferably 150 or less. The lower limit is not particularly limited, but is preferably 30 or more, and more preferably 40 or more.

[0156] The alcohol may have an etheric oxygen atom in the molecule. The etheric oxygen atom refers to an oxygen atom present between carbon-carbon bonds in the molecule. Examples of the alcohol having an etheric oxygen atom in the molecule include dialkylene glycol, trialkylene glycol, polyalkylene glycol, alkylene glycol monoalkyl ether, dialkylene glycol monoalkyl ether, trialkylene glycol monoalkyl ether and polyalkylene glycol monoalkyl ether.

[0157] Examples of the alcohol include 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, lauryl alcohol, 1-decanol, 1-nonanol, 1-octadecanol, methanol, ethanol, 2-ethylhexanol, isopropanol, 2-butanol, isobutanol, 3-methyl-1-butanol, tert-butanol, 2-pentanol, tert-pentanol, 4-methyl-2-pentanol, 2-hexanol, cyclopentanol, 2-heptanol, 2-octanol, 2-ethylpentanol, 4-octanol, 3-methoxy-3-methyl- Monoalcohols such as 1-butanol, 3-methoxy-1-butanol and 1-methoxy-2-butanol, propylene glycol, ethylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tetraethylene glycol, 2-methyl-1,3-propanediol, 1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 2,3-butanediol, hexanediol, pinacol and diols such as 1,3-cyclopentanediol, and polyols such as glycerol are preferred, and diols are preferred.

[0158] Among them, the alcohol is preferably propylene glycol, ethylene glycol, diethylene glycol, dipropylene glycol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, lauryl alcohol, 1-octadecyl alcohol, 2-ethylhexanol or 2-octanol, more preferably propylene glycol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol or 2-ethylhexanol, further preferably propylene glycol, ethylene glycol, diethylene glycol or dipropylene glycol, and particularly preferably propylene glycol or dipropylene glycol.

[0159] The alcohol may be used alone or in combination of two or more.

[0160] The alcohol content is 5 to 200 ppm by mass relative to the total mass of the chemical solution, and is preferably 10 to 150 ppm by mass, more preferably 30 to 120 ppm by mass, and even more preferably 30 to 100 ppm by mass from the viewpoint of achieving more excellent effects of the present invention.

[0161] When the content of alcohol exceeds 200 mass ppm or is less than 5 mass ppm relative to the total mass of the chemical solution, the contact angle of water decreases, which is not preferable in that the effect of the present invention is deteriorated.

[0162] The alcohol content can be measured using GC-MS (Gas Chromatography Mass Spectrometry) or the like.

[0163] 〔water〕

[0164] The chemical solution of the first aspect and the second aspect may contain water.

[0165] The water is not particularly limited, and examples thereof include distilled water, ion-exchanged water, pure water, and ultrapure water. Ultrapure water is preferred.

[0166] However, from the perspective of achieving a more excellent effect of the present invention, the water content relative to the total mass of the liquid medicine is preferably 300 mass ppm or less, more preferably 200 mass ppm or less, further preferably 100 mass ppm or less, particularly preferably 30 mass ppm or less, and most preferably 10 mass ppm or less. The lower limit is not particularly limited, but is preferably 1 mass ppm or more, and more preferably 5 mass ppm or more.

[0167] Water may be intentionally added, may be inevitably contained in the chemical solution, or may be inevitably contained during the production, storage and / or transfer of the chemical solution.

[0168] The method for adjusting the water content is not particularly limited, and examples thereof include a method of adding water, a method of removing water from the drug solution and / or a raw material used in the preparation of the drug solution, and a combination thereof.

[0169] As a method for removing water, a known dehydration method can be used. Examples of the dehydration method include distillation, dehydration using a water adsorbent, and dehydration using a dehydration membrane.

[0170] The water content can be measured using a device using the Karl Fischer water content determination method as the determination principle. As the above-mentioned device, for example, "CA-200" (manufactured by Mitsubishi Chemical Analytech Co., Ltd.) and "MKC-710M" (manufactured by KYOTO ELECTRONICS MANUFACTURING C0., LTD.) can be used.

[0171] [Other ingredients]

[0172] The drug solution of the first embodiment and the second embodiment may contain other components in addition to the above-mentioned components. Examples of other components include acidic compounds and basic compounds.

[0173] The acidic compound is a compound that is acidic (pH less than 7.0) in aqueous solution, and examples thereof include inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, hydrobromic acid and hydrofluoric acid, and organic acids such as p-toluenesulfonic acid, benzenesulfonic acid, methanesulfonic acid and trifluoromethanesulfonic acid.

[0174] The basic compound is a compound that is alkaline (pH over 7.0) in aqueous solution, and examples thereof include inorganic bases such as lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, calcium hydroxide, strontium hydroxide, and barium hydroxide, and organic bases such as pyridine and quaternary ammonium salts.

[0175] The acidic compound and the basic compound may be used alone or in combination of two or more.

[0176] [Method for producing liquid medicine]

[0177] <Liquid Preparation Process>

[0178] The method for producing the drug solution of the present invention is not particularly limited, and it can be produced, for example, by mixing the above-mentioned components. The order or time of mixing the components and the order and time are not particularly limited. For example, a method for producing the drug solution of the first embodiment by adding a silylating agent and an alcohol to a stirring machine such as a mixer to which a purified aprotic solvent is added and then stirring the mixture sufficiently can be cited.

[0179] The manufacturing process of the chemical solution of the present invention may include a step selected from a distillation step of distilling a raw material, a dehydration step of dehydrating the chemical solution, a metal removal step of removing metal components from the chemical solution, a filtration step of filtering the chemical solution, and a destaticization step of destaticizing the chemical solution.

[0180] <Container>

[0181] As the container for storing the chemical solution, for example, a well-known container can be used.

[0182] The container is preferably a semiconductor-dedicated container with high cleanliness and little elution of impurities.

[0183] Examples of the container include the "Clean Bottle" series (manufactured by AICELLO CORPORATION) and the "Pure Bottle" (manufactured by KODAMA PLASTICS Co., Ltd.). In addition, from the perspective of preventing impurities from being mixed (contaminated) into the raw materials and the chemical solution, it is also preferable to use a multilayer container having a six-layer structure in which the inner wall of the container is composed of six kinds of resins or a multilayer container having a seven-layer structure composed of seven kinds of resins.

[0184] Examples of the multilayer container include the container described in Japanese Patent Application Laid-Open No. 2015-123351, and the contents thereof are incorporated into this specification.

[0185] Examples of the material of the inner wall of the container include at least one first resin selected from polyethylene resin, polypropylene resin, and polyethylene-polypropylene resin, a second resin different from the first resin, and metals such as stainless steel, Hastelloy, Inconel, and Monel. Preferably, the inner wall of the container is formed or coated with the above materials.

[0186] The second resin is preferably a fluororesin (perfluororesin). When a fluororesin is used, it is preferred because it can suppress the elution of ethylene or propylene oligomers.

[0187] Examples of the container include FluoroPure PFA composite drum (manufactured by Entegris Corporation), page 4 of JP-A-3-502677, page 3 of WO 2004 / 016526, and pages 9 and 16 of WO 99 / 046309.

[0188] As the inner wall of the container, quartz and electrolytically polished metal materials are also preferred, in addition to fluororesins.

[0189] As the stainless steel, for example, known stainless steel can be mentioned.

[0190] Among them, stainless steel containing 8 mass % or more of Ni is preferred, and austenitic iron-based stainless steel containing 8 mass % or more of Ni is more preferred.

[0191] As the Ni—Cr alloy, for example, a known Ni—Cr alloy can be mentioned.

[0192] Among them, a Ni—Cr alloy having a Ni content of 40 to 75% by mass and a Cr content of 1 to 25% by mass is preferred.

[0193] The Ni—Cr alloy may further contain boron, silicon, tungsten, molybdenum, copper or cobalt in addition to the above alloys as needed.

[0194] As a method for electrolytically polishing a metal material, for example, a known method can be cited, specifically, the method described in paragraphs

[0011] to

[0014] of Japanese Patent Application Laid-Open No. 2015-227501 and paragraphs

[0036] to

[0042] of Japanese Patent Application Laid-Open No. 2008-264929, and these contents are incorporated into this specification.

[0195] The metal material is preferably polished. As a method of polishing, for example, a known method can be mentioned.

[0196] The size of the abrasive grains used in the fine polishing is preferably not more than #400 because the surface irregularities of the metal material are likely to become smaller. The polishing is preferably performed before the electrolytic polishing.

[0197] The metal material may be processed by combining one or more of polishing, pickling, magnetic fluid polishing, etc., performed in multiple stages by changing the size of the abrasive grains or the like.

[0198] It is preferable to clean the inside of the container before filling the container with the chemical solution.

[0199] The liquid used for cleaning can be appropriately selected depending on the application, and is preferably a liquid containing at least one of a chemical solution or a component added to a chemical solution.

[0200] In order to prevent the change of the components in the liquid medicine during storage, the inside of the container can be replaced with an inert gas (e.g., nitrogen and argon) with a purity of 99.99995% by volume or more. In particular, a gas with a low water content is preferred. In addition, when transporting and storing the container containing the liquid medicine, it can be either at room temperature or at a controlled temperature. Among them, in order to prevent deterioration, it is preferred to control the temperature within the range of -20 to 20°C.

[0201] 〔Use of the liquid medicine〕

[0202] The chemical solution of the present invention is preferably a chemical solution used in the manufacture of semiconductors, and is used for treating a modified substrate. Through the above treatment, a modified substrate having a film containing silicon atoms formed on the surface of the modified substrate is obtained. In addition, the silicon atoms contained in the film containing silicon atoms are silicon atoms derived from the above silylating agent or the specific silicon compound.

[0203] The method for treating the substrate is not particularly limited, and may be a method of bringing a chemical solution into contact with the substrate to be modified. The method for producing the modified substrate will be described later.

[0204] <Modified substrate>

[0205] The substrate to be modified is preferably a substrate having a region made of an insulator.

[0206] It is preferred that the region composed of the insulator has a functional group on the surface.

[0207] The functional group is a functional group that reacts when in contact with the silylating agent or the specific silicon compound to introduce a silyl group, and examples thereof include a hydroxyl group, an amino group, a carboxyl group, and an amide group, and a hydroxyl group is preferred.

[0208] As the above-mentioned insulator, metal oxide is preferable.

[0209] Examples of the metal contained in the metal oxide include silicon (Si), aluminum (Al), tantalum (Ta), zirconium (Zr), and lanthanum (La). In the present specification, Si is a metal.

[0210] As the above-mentioned metal oxide, silicon oxide is preferred. Specifically, for example, SiO y The material represented by the composition (y preferably represents 0.5 to 2.0, more preferably represents 1.0 to 2.0.) and SiO z C w A material represented by a composition of (z preferably represents 0.5 to 2.0, more preferably represents 1.0 to 2.0, and w preferably represents 0.5 to 2.0, more preferably represents 1.0 to 2.0.) SiO y The composition of the material and SiO z C w The material represented by the composition may further contain hydrogen. z C w The material represented by the composition can be, for example, Si(OC2H5)4 (tetraethyl orthosilicate, TEOS).

[0211] Among them, as silicon oxide, a material represented by a composition of SiO2 (silicon dioxide) or TEOS is preferred.

[0212] The method for forming the region composed of the insulator is not particularly limited, and a known method can be used, for example, CVD, physical vapor deposition, plasma irradiation, heat treatment of a silicon substrate, and coating of a precursor compound.

[0213] The modified substrate may have another region different from the region composed of the above-mentioned insulator.

[0214] As the other region, for example, a conductive metal region can be cited.

[0215] The type of metal contained in the above-mentioned metal area is not particularly limited, and for example, at least one metal selected from aluminum (Al), copper (Cu), ruthenium (Ru), cobalt (Co), tungsten (W), titanium (Ti), tantalum (Ta), chromium (Cr), hafnium (Hf), osmium (Os), platinum (Pt), nickel (Ni), manganese (Mn), iron (Fe), zirconium (Zr), molybdenum (Mo), palladium (Pd), lanthanum (La) and iridium (Ir) can be mentioned.

[0216] The metal region may be any one of a single substance and an alloy of the metal. Furthermore, the metal region may contain elements other than the metal. Examples of elements other than the metal include hydrogen, phosphorus, and nitrogen.

[0217] It is also preferred that the surface of the other region does not have the functional group.

[0218] The method for forming the region composed of the above-mentioned metal material is not particularly limited, and a known method can be used, for example, a CVD method, electroplating, and a physical vapor deposition method.

[0219] The modified substrate preferably has at least two regions made of different materials on its surface.

[0220] There is no particular limitation on the modified substrate having at least two or more regions composed of the above-mentioned different materials on its surface. For example, there can be cited a substrate having a region composed of an insulator and a metal region composed of a conductive metal material, and a substrate having two or more regions respectively composed of different insulators. Preferably, it is a substrate having a region composed of an insulator and a metal region composed of a conductive metal material.

[0221] It is preferred that the film containing silicon atoms formed by the above-mentioned treatment functions as a mask when a material is deposited on the modified substrate by the ALD treatment. That is, when the modified substrate is subjected to the ALD treatment, it is preferred that the material is not deposited in the region where the film containing silicon atoms formed by the chemical solution of the present invention is formed, and the material is deposited in the region where the film containing silicon atoms is not formed.

[0222] However, from the viewpoint of achieving a more excellent effect of the present invention, the contact angle of water of the film containing silicon atoms is preferably 70° or more, more preferably 80° or more, and further preferably 90° or more. The upper limit is not particularly limited, but is usually 120° or less.

[0223] The contact angle of water is measured in the following manner.

[0224] The contact angle of a water droplet after contact with the surface of the object for 500 milliseconds was measured three times using a contact angle meter (DMs-501, manufactured by Kyowa Interface Science Co., Ltd.), and the average value was taken as the contact angle.

[0225] <Method for Manufacturing Modified Substrate>

[0226] [Step 1: Preparation of modified substrate]

[0227] The method for producing a modified substrate of the present invention includes step 1 of bringing the region of the substrate made of the insulator into contact with the chemical solution of the present invention to form a film containing silicon atoms on the region made of the insulator.

[0228] The contact method is not particularly limited, and a known method can be used. For example, a method of coating or spraying a chemical solution on the modified substrate and a method of immersing the modified substrate in the chemical solution can be cited. When the substrate is immersed in the chemical solution, the chemical solution can be convected.

[0229] The temperature of the drug solution during contact is not particularly limited, but is preferably 10 to 50°C.

[0230] The contact time between the chemical solution and the modified substrate is not particularly limited, but is preferably 10 seconds to 10 hours, more preferably 30 seconds to 1 hour, and even more preferably 1 minute to 30 minutes.

[0231] The chemical solution may be brought into contact with the substrate to be modified and then heated. The solvent contained in the chemical solution may be removed by heating, and the film containing silicon atoms may be made denser.

[0232] The heating temperature is not particularly limited, but is preferably 50 to 300°C, more preferably 60 to 180°C.

[0233] The heating method is not particularly limited, and examples thereof include a method of contacting with a heating element (for example, heating with a hot plate) and a method of irradiating with infrared rays.

[0234] In addition, the substrate to be modified may be subjected to pretreatment before step 1. Examples of the pretreatment include surface activation treatment and cleaning treatment.

[0235] Examples of the surface activation treatment include a treatment in contact with a treatment liquid, a plasma treatment, a corona treatment, and an ozone treatment.

[0236] As a method for contacting the above-mentioned treatment liquid, it is preferable to immerse the modified substrate in the treatment liquid in the same method as the method for contacting the modified substrate with the chemical solution. In addition, during immersion, the treatment liquid can be convected.

[0237] As the above-mentioned treatment liquid, an aqueous solution containing an acidic compound can be cited. As the acidic compound, hydrogen fluoride, hexafluorosilicic acid, hexafluorotitanic acid, hexafluorozirconic acid, hexafluorophosphoric acid, tetrafluoroboric acid and salts thereof can be cited, preferably hydrogen fluoride. As the content of the acidic compound, it is preferably 0.01 to 5% by mass, more preferably 0.1 to 2% by mass, and further preferably 0.1 to 5% by mass relative to the total mass of the treatment liquid.

[0238] The temperature of the treatment liquid during contact is not particularly limited, but is preferably 10 to 60°C.

[0239] The contact time between the treatment liquid and the modified substrate is not particularly limited, but is preferably 10 seconds to 10 hours, more preferably 10 seconds to 1 hour, and further preferably 30 seconds to 30 minutes.

[0240] The methods of the plasma treatment and the ozone treatment are not particularly limited, and known methods can be used.

[0241] The cleaning treatment may include contacting a cleaning solution such as water or an organic solvent with the substrate to be modified. The cleaning solution may be contacted with the substrate to be modified by the same method as the contacting of the treatment solution with the substrate to be modified.

[0242] By performing the above-mentioned pretreatment, it is conceivable that the inactivated functional groups are activated and / or impurities on the surface of the modified substrate are removed, the reaction between the silylating agent or the specific silicon compound and the surface of the modified substrate is promoted, and the coverage rate of the film containing silicon atoms is increased.

[0243] [Step 2: Rinse treatment]

[0244] The method for producing a modified substrate of the present invention preferably includes step 2 of rinsing the substrate having the film containing silicon atoms formed thereon after step 1. The rinsing treatment can remove chemical solution components and / or impurities adhering to areas other than the predetermined area.

[0245] The rinsing method is not particularly limited, and a method of bringing the rinsing liquid into contact with the substrate on which the film containing silicon atoms is formed can be cited. As the contact method, the same method as the method of bringing the above-mentioned chemical solution into contact with the modified substrate can be cited. The temperature during the contact is not particularly limited, but is preferably 10 to 50°C.

[0246] The rinse liquid is not particularly limited, and a known organic solvent can be used. Examples of the organic solvent include the above-mentioned alcohols and aprotic solvents.

[0247] [Method for producing laminated body]

[0248] [Step 3: ALD treatment]

[0249] The method for producing a laminate of the present invention includes step 3 of subjecting the modified substrate to an ALD treatment to form a metal film, a metal oxide film or a metal nitride film on a region other than a region where a film containing silicon atoms is formed.

[0250] Through the above-mentioned step 3, a stacked body is obtained, which has a coating containing silicon atoms on the region composed of an insulator of a substrate having a region composed of an insulator, and has a film formed by material deposition based on ALD processing on the region other than the region composed of the insulator.

[0251] The modified substrate may be a substrate on which a film containing silicon atoms is formed on a region formed of an insulator in the step 1 , or may be a substrate that has undergone another step such as step 2 after the step 1 .

[0252] The method of ALD treatment is not particularly limited, and a known method can be used.

[0253] For example, a method can be cited in which a gas of a precursor (precursor) which will be the raw material for a film (ALD film) to be formed by depositing material through ALD processing is supplied to the surface of a modified substrate, and then the raw material is decomposed and / or chemically reacted by an oxidant or the like to deposit the material to form an ALD film.

[0254] The precursor is not particularly limited, and a known precursor may be used depending on the type of ALD film to be formed, and examples thereof include organic metal compounds. As the precursor, compounds described in paragraphs

[0021] to

[0025] of JP-A-2022-080800 may be used.

[0255] The oxidizing agent is not particularly limited, and any known oxidizing agent used in an ALD process can be used, and examples thereof include water, oxygen, and ozone.

[0256] The material constituting the ALD film can be controlled by the type of precursor supplied, the supply atmosphere, the oxidant, and the like.

[0257] The material of the formed ALD film is not particularly limited, and examples thereof include metals, metal oxides, and metal nitrides. Examples of metals include aluminum, titanium, chromium, iron, cobalt, nickel, copper, zinc, yttrium, zirconium, niobium, molybdenum, ruthenium, palladium, lanthanum, cerium, hafnium, tantalum, tungsten, platinum, and bismuth. Examples of metal oxides include aluminum oxide, titanium oxide, zinc oxide, zirconium oxide, hafnium oxide, and tantalum oxide. Examples of metal nitrides include titanium nitride and tantalum nitride.

[0258] In the ALD process, a process for modifying the surface of a region where a film containing silicon atoms is not formed may be performed.

[0259] After the ALD treatment, the thickness of the material deposited on the film containing silicon atoms is preferably as thin as possible, preferably 4.0 nm or less, more preferably 2.0 nm or less, and further preferably 1.0 nm or less. The lower limit is not particularly limited, but is 0 nm.

[0260] When a material is deposited on a region where a film containing silicon atoms is not formed by ALD treatment, the ratio of the thickness of the material deposited on the region where a film containing silicon atoms is formed to the thickness of the material deposited on the region where a film containing silicon atoms is not formed is preferably 0.75 or less, more preferably 0.5 or less, and further preferably 0.25 or less. The lower limit of the above ratio may be 0, or may be 0.

[0261] [Step 4: Removal of film]

[0262] The method for producing a laminate of the present invention may include step 4 of removing the film containing silicon atoms from the laminate obtained in step 3. Through step 4, a laminate is obtained in which no layer exists on the region composed of the insulator and the ALD film is formed only on the region other than the region composed of the insulator.

[0263] The method for removing the film containing silicon atoms is not particularly limited, and examples thereof include dry etching, wet etching, and a combination thereof.

[0264] As dry etching, there can be cited a method of supplying reactive ions or reactive radicals to the surface of a laminate having a film containing silicon atoms. The reactive ions or reactive radicals can be generated by plasma or the like, preferably using a mixed gas containing one or more gases selected from oxygen, nitrogen and hydrogen. The mixed gas may contain a rare gas. In addition, dry etching may be physical etching using a sputtering phenomenon.

[0265] In wet etching, it is sufficient to supply an etching solution to the surface of the laminate having a film containing silicon atoms. Examples of the etching solution include an etching solution containing an oxidizing agent such as ozone and an etching solution containing an organic solvent. Examples of the organic solvent in the etching solution containing an organic solvent include the organic solvent contained in the above-mentioned chemical solution, preferably a hydrocarbon solvent.

[0266] The film containing the silicon atoms also preferably functions as a mask when forming a metal-containing film by a chemical vapor deposition method (CVD) other than the ALD process. That is, in the CVD process, the deposition of a CVD-based film (hereinafter also referred to as a "CVD film") is suppressed in the region where the film containing the silicon atoms is formed, and the CVD film can be deposited in the region where the film containing the silicon atoms is not formed. In this way, the film containing the silicon atoms functions as a mask in the formation of the CVD film, and a stacked body in which the CVD film is selectively formed in the region other than the region where the film containing the silicon atoms is formed is obtained.

[0267] Examples of CVD other than ALD that can be preferably used for the modified substrate include known methods such as thermal CVD and plasma CVD. Examples of the raw material of the CVD film used in the CVD process include the materials listed as the raw materials of the ALD film.

[0268] Example

[0269] Hereinafter, the present invention will be described in further detail based on examples.

[0270] The materials, usage amounts, ratios, processing contents and processing steps shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention should not be interpreted in a limiting sense by the following examples.

[0271] The preparation, filling, and storage of the chemical solution were all performed in a clean room that meets the ISO Class 2 standard or below. The containers used were cleaned with the solvent used in the preparation or the prepared chemical solution before use.

[0272] [Preparation of drug solution]

[0273] The chemical solutions used in Examples and Comparative Examples were prepared by adding the components (silylation agent or specific silicon compound, alcohol and water) to an aprotic solvent in the amounts shown in the following table. The components used in the preparation of the chemical solutions are shown below.

[0274] In addition, super dehydrated grade was used as aprotic solvent and alcohol.

[0275] 〔Silylating agent or specific silicon compound〕

[0276] TMDS (Tetramethyldisilazane)

[0277] ·HMDS (hexamethyldisilazane)

[0278] ·Butyldimethyl(dimethylamino)silane

[0279] Octadecyltrimethoxysilane

[0280] 〔Aprotic solvent〕

[0281] Propylene carbonate

[0282] ·Ethylene glycol dibutyl ether

[0283] γ-Butyrolactone

[0284] 〔alcohol〕

[0285] Propylene glycol

[0286] 1-Propanol

[0287] 1-Pentanol

[0288] 1-Octanol

[0289] 2-Ethylhexanol

[0290] ·Lauryl alcohol

[0291] 1-Octadecanol

[0292] ·Dipropylene glycol

[0293] The alcohol content in the chemical solution was confirmed using a GC / MS device (GC / MS-QP2020 manufactured by Shimadzu Corporation). The measurement conditions are as follows.

[0294] Column: DB-Wax UI (length 30 m, inner diameter 0.25 mm, film thickness 0.25 μm, manufactured by Agilent Technologies, Inc.)

[0295] Column temperature setting: 40℃(2min)-15℃ / min-250℃(6min)

[0296] Injection volume: 1μL (250℃, split ratio 1 / 50)

[0297] Flow rate: 1.11 mL / min

[0298] Detector: EI-MS (m / z 20-600)

[0299] The water content (water content) in the liquid was confirmed using a Karl Fischer apparatus (micro-water measuring apparatus, CA-200, manufactured by Mitsubishi Chemical Analytech Co., Ltd.). Specifically, Aquamicron AX was used for the anolyte and Aquamicron CXU was used for the catholyte, and the amount of water vaporized from the sample was measured by the coulometric titration-heating vaporization method (vial method). The heating temperature was set to 140°C.

[0300] [Preparation of modified substrate]

[0301] According to the following procedure, a film was formed on a substrate using the chemical solutions of Examples and Comparative Examples.

[0302] As a substrate having an insulating region, a silicon oxide layer was formed on one surface of a commercially available silicon wafer (diameter: 12 inches) by CVD. The processing time of the CVD method was adjusted so that the film thickness of the silicon oxide layer would be 100 nm.

[0303] The obtained wafer with silicon oxide layer was cut into 2 cm squares. The cut wafer was immersed in a container filled with 0.1 mass % hydrogen fluoride aqueous solution and pre-treated. The pre-treatment was carried out while stirring the aqueous solution at a stirring speed of 250 rpm, the temperature of the aqueous solution was set to 25° C., and the immersion time was set to 1 minute. Nitrogen gas was blown to the pre-treated wafer to dry it.

[0304] Next, each wafer subjected to pretreatment was immersed in each chemical solution to form a film containing silicon atoms. The film formation was performed while stirring the aqueous solution at a stirring speed of 250 rpm, the temperature of the chemical solution was set at 25° C., and the immersion time was set at 10 minutes.

[0305] Finally, the obtained wafer was rinsed by immersing it in isopropyl alcohol (IPA). The rinsing was performed while stirring the IPA at a stirring speed of 250 rpm, the temperature of the IPA was set to 25° C., and the rinsing time was set to 30 seconds. Nitrogen gas was blown to the rinsed wafer to dry it.

[0306] Through the above-described procedures, a modified substrate having a film containing silicon atoms formed thereon was obtained.

[0307] [evaluate]

[0308] [Contact angle evaluation]

[0309] The water contact angle of the obtained modified substrate was measured by the following method.

[0310] The contact angle was measured three times using a contact angle meter (DMs-501, manufactured by Kyowa Interface Science Co., Ltd.) after the water droplet was in contact with the surface for 500 milliseconds, and the average value was used as the contact angle. In addition, the surface tension of water was set to 72.9 mN / m and analyzed. The measurement was performed in an environment of 23°C.

[0311] [Evaluation of deposition amount (film thickness)]

[0312] The obtained modified substrate was subjected to an ALD method using an atomic layer deposition apparatus (AD-230LP, manufactured by Samco Inc.). Trimethylaluminum was used as an organic metal raw material, water was used as an oxidant, and the ALD treatment temperature was set to 150° C. Other conditions were adjusted to a film thickness of 5 nm.

[0313] The film thickness of the aluminum oxide layer of each sample after ALD treatment was measured using a spectroscopic ellipsometer (M-2000XI, manufactured by JA Woollam Japan Co., Inc.). The film thickness was measured at 5 points of the sample, and the average value was taken as the film thickness. The measurement range was set to 1.2-2.5 eV, and the measurement angle was set to 70° and 75°.

[0314] In addition, the smaller the film thickness is, the more difficult it is to deposit the film by the ALD process.

[0315] [result]

[0316] Table 1 shows the components of the chemical solutions and the evaluation results.

[0317] In the table, "wt%" means the mass % concentration relative to the total mass of the chemical solution, and "ppm" means the mass ppm concentration relative to the total mass of the chemical solution.

[0318] In the table, the alcohol content and water content are values ​​measured by the above-mentioned method.

[0319] The remainder after removing the silylating agent or the specific silicon compound, the alcohol, and water from the chemical solution is an aprotic solvent.

[0320] In the table, "propylene carbonate / ethylene glycol dibutyl ether = 1 / 1" means a case where a mixed solvent of propylene carbonate and ethylene glycol dibutyl ether in a mass ratio of propylene carbonate / ethylene glycol dibutyl ether = 1 / 1 is used as an aprotic solvent, and "propylene carbonate / γ-butyrolactone = 1 / 1" means a case where a mixed solvent of propylene carbonate and γ-butyrolactone in a mass ratio of propylene carbonate / γ-butyrolactone = 1 / 1 is used as an aprotic solvent.

[0321] [Table 1]

[0322]

[0323] From the results in Table 1, it can be confirmed that the chemical solution of the present invention can form a film that can suppress the deposition of materials by the ALD process.

[0324] From the results of Examples 1 to 6, it was confirmed that the effect of the present invention is more excellent in the case of the silazane compound.

[0325] From the results of Examples 1 and 7 to 10, it was confirmed that when the aprotic solvent was a carbonate solvent, the effect of the present invention was more excellent.

[0326] From the results of Examples 11 to 14, it was confirmed that the effect of the present invention is more excellent when the content of alcohol is 10 to 150 ppm by mass based on the total mass of the chemical solution.

[0327] From the results of Examples 15 to 22, it was confirmed that the effect of the present invention is more excellent when the alcohol has two or more hydroxyl groups.

[0328] From the results of Examples 15 to 22, it was confirmed that when the number of carbon atoms of the alcohol was 10 or less, the effect of the present invention was more excellent.

[0329] From the results of Examples 23 to 25, it can be confirmed that when the water content is 200 mass ppm or less, the effect of the present invention is more excellent, when it is 100 mass ppm or less, the effect of the present invention is further excellent, and when it is 10 mass ppm or less, the effect of the present invention is particularly excellent.

[0330] From the results of Examples 1 and 26 to 28, it can be confirmed that the effect of the present invention is more excellent when the content of the silylating agent or the specific silicon compound is 0.1 to 5 mass % relative to the total mass of the chemical solution, and the effect of the present invention is further excellent when it is 0.3 to 3 mass %.

Claims

1. A chemical solution used in the manufacture of a semiconductor, comprising: silylating agent, aprotic solvent and alcohol, The content of the alcohol is 5 ppm by mass to 200 ppm by mass relative to the total mass of the chemical solution.

2. The liquid medicine according to claim 1, wherein The silylating agent contains a compound having a Si—N bond.

3. The liquid medicine according to claim 1, wherein The silylating agent contains a silazane compound or a compound represented by formula (1), R 1 Each independently represents a hydrocarbon group optionally having a halogen atom, R 2 Each independently represents a hydrogen atom, a hydrocarbon group optionally having a halogen atom, or an acyl group optionally having a halogen atom, and a represents an integer of 1 to 3.

4. The liquid medicine according to claim 1, wherein The silylating agent contains a silazane compound.

5. The liquid medicine according to claim 1, wherein The liquid further contains water, The water content is 100 ppm by mass or less relative to the total mass of the chemical solution.

6. The liquid medicine according to claim 1, wherein The alcohol has 10 or less carbon atoms.

7. The liquid medicine according to claim 1, wherein The alcohol has two or more hydroxyl groups.

8. The liquid medicine according to claim 1, wherein The content of the alcohol is 5 ppm by mass to 150 ppm by mass based on the total mass of the chemical solution.

9. A chemical solution used in the manufacture of a semiconductor, comprising: a compound selected from the group consisting of silazane compounds, compounds represented by formula (1) and alkoxysilane compounds, an aprotic solvent and an alcohol, The content of the alcohol is 5 ppm to 200 ppm by mass relative to the total mass of the chemical solution. R 1 Each independently represents a hydrocarbon group optionally having a halogen atom, R 2 Each independently represents a hydrogen atom, a hydrocarbon group optionally having a halogen atom, or an acyl group optionally having a halogen atom, and a represents an integer of 1 to 3. 10 . The chemical solution according to claim 1 , which is used for treating a substrate having at least two regions composed of different materials on its surface.

11. A method for manufacturing a modified substrate, comprising step 1, in which a substrate having a region composed of an insulator is brought into contact with the chemical solution according to any one of claims 1 to 10 to form a film containing silicon atoms on the region composed of the insulator.

12. The method for manufacturing a modified substrate according to claim 11, wherein: The insulator is a metal oxide. 13 . The method for producing a modified substrate according to claim 11 , further comprising, after the step 1 , a step 2 of performing a rinsing treatment on the substrate having the film containing the silicon atoms.

14. A method for manufacturing a stacked body, comprising step 3, in which an atomic layer deposition process is performed on a modified substrate manufactured using the manufacturing method described in claim 11 to form a metal film, a metal oxide film or a metal nitride film on an area other than an area where a film containing the silicon atoms is formed. 15 . The method for producing a laminated body according to claim 14 , further comprising, after the step 3 , a step 4 of removing the film containing the silicon atoms.

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